Chi-Kung Ni

H atom elimination from the πσ* state in the photodissociation of phenol

Photodissociation of phenol at 248 nm was studied using multimass ion imaging techniques. Photofragment translational energy distribution of H atom elimination was measured. The results demonstrate that H atom elimination occurs on the πσ* excited state which has repulsive potential-energy functions with respect to the stretching of OH bond. It supports the recent ab initio calculation.

Dissociation rate of hot benzene

The dissociation rate of benzene and d6-benzene were measured under collision-free condition by multimass ion imaging techniques. The value of 1±0.2×105 s−1 and 5±1×104 s−1 were obtained for benzene and d6-benzene, respectively, with internal energy of 618 kJ/mol. The dissociation rate of benzene with internal energy of 483 kJ/mol was too slow to be measured, and the upper limit of the dissociation rate was estimated to be 3×103 s−1.

Multimass ion imaging detection: Application to photodissociation

A constant momentum mass spectrometer with a two-dimensional ion detector in conjunction with a pulsed vacuum ultraviolet laser is used for the simultaneous measurement of the translational energy distributions of many different fragments. A description of the apparatus and its performance are presented. Preliminary experimental results on the photodissociation of toluene and benzene are given.

Photodissociation dynamics of indole in a molecular beam

Photodissociation of indole at 193 and 248 nm under collision-free conditions has been studied in separate experiments using multimass ion imaging techniques. H atom elimination was found to be the only dissociation channel at both wavelengths. The photofragment translational energy distribution obtained at 193 nm contains a fast and a slow component. Fifty-four percent of indole following the 193 nm photoexcitation dissociate from electronically excited state, resulting in the fast component. The rest of 46% indole dissociate through the ground electronic state, giving rise to the slow component. A dissociation rate of 6 x 10(5) s(-1), corresponding to the dissociation from the ground electronic state, was determined. Similar two-component translational energy distribution was observed at 248 nm. However, more than 80% of indole dissociate from electronically excited state after the absorption of 248 nm photons. A comparison with the potential energy surfaces from the ab initio calculation has been made.

Supercollisions and energy transfer of highly vibrationally excited molecules

Collisional energy-transfer probability distribution functions of highly vibrationally excited molecules and the existence of supercollisions remain as the outstanding questions in the field of intermolecular energy transfer. In this investigation, collisional interactions between ground state Kr atoms and highly vibrationally excited azulene molecules (4.66 eV internal energy) were examined at a collision energy of 410 cm-1 using a crossed molecular beam apparatus and time-sliced ion imaging techniques. A large amount of energy transfer (1000-5000 cm-1) in the backward direction was observed. We report the experimental measurement for the shape of the energy-transfer probability distribution function along with a direct observation of supercollisions.

Ring opening dissociation of d6-benzene

The photodissociation of jet-cooled d6-benzene at 193 nm was studied. Photofragment translational energy distributions were measured by multimass ion imaging techniques. In addition to the major channel of D atom elimination from one-photon excitation, elimination of two D atoms and two ring opening dissociation channels, C6D6→CD3+C5D3 and C6D6→C2D3+C4D3, resulting from two-photon dissociation was observed. These ring opening channels were confirmed by the momentum match between the two fragments in each channel.

Ion‐to‐neutral ratio of 2,5‐dihydroxybenzoic acid in matrix‐assisted laser desorption/ionization

RATIONALE In most previous studies, the ratios of desorbed ions and neutrals from matrix-assisted laser desorption/ionization (MALDI) were measured outside the common MALDI conditions. In this work, we measured the ratios under common MALDI conditions. METHODS Ions were detected using a time-of-flight mass spectrometer in combination with a time-gated ion imaging detector. Mass-resolved desorbed neutral molecules at different angles and velocities were measured using a modified crossed molecular beam apparatus. RESULTS The upper limit of the ion-to-neutral ratio from pure 2,5-dihydroxybenzoic acid (25DHB) is 4 × 10(-9) at laser fluence 40 J/m(2), it increases to 3 × 10(-7) at laser fluence 250 J/m(2). The ratios of matrix from the mixture of 25DHB and analyte remain in the same order of magnitude as pure 25DHB. However, the ratio of analyte depends strongly on the analyte. Values as large as 10(-3)-10(-4) for bradykinin and as small as <10(-8) for glycine were observed at laser fluence ~100 J/m(2). CONCLUSION The ion-to-neutral ratios of 25DHB matrix measured in this work are much smaller than some of the values reported in previous work using different methods and/or under different MALDI conditions.

Photodissociation dynamics of nitrobenzene and o-nitrotoluene

Photodissociation of nitrobenzene at 193, 248, and 266 nm and o-nitrotoluene at 193 and 248 nm was investigated separately using multimass ion imaging techniques. Fragments corresponding to NO and NO(2) elimination from both nitrobenzene and o-nitrotoluene were observed. The translational energy distributions for the NO elimination channel show bimodal distributions, indicating two dissociation mechanisms involved in the dissociation process. The branching ratios between NO and NO(2) elimination channels were determined to be NONO(2)=0.32+/-0.12 (193 nm), 0.26+/-0.12 (248 nm), and 0.4+/-0.12(266 nm) for nitrobenzene and 0.42+/-0.12(193 nm) and 0.3+/-0.12 (248 nm) for o-nitrotoluene. Additional dissociation channels, O atom elimination from nitrobenzene, and OH elimination from o-nitrotoluene, were observed. New dissociation mechanisms were proposed, and the results are compared with potential energy surfaces obtained from ab initio calculations. Observed absorption bands of photodissociation are assigned by the assistance of the ab initio calculations for the relative energies of the triplet excited states and the vertical excitation energies of the singlet and triplet excited states of nitrobenzene and o-nitrotoluene. Finally, the dissociation rates and lifetimes of photodissociation of nitrobenzene and o-nitrotoluene were predicted and compared to experimental results.

Energy transfer of highly vibrationally excited azulene. III. Collisions between azulene and argon.

The energy transfer dynamics between highly vibrationally excited azulene molecules (37 582 cm(-1) internal energy) and Ar atoms in a series of collision energies (200, 492, 747, and 983 cm(-1)) was studied using a crossed-beam apparatus along with time-sliced velocity map ion imaging techniques. The angular resolved collisional energy-transfer probability distribution functions were measured directly from the scattering results of highly vibrationally excited azulene. Direct T-VR energy transfer was found to be quite efficient. In some instances, nearly all of the translational energy is transferred to vibrational/rotational energy. On the other hand, only a small fraction of vibrational energy is converted to translational energy (V-T). Significant amount of energy transfer from vibration to translation was observed at large collision energies in backward and sideway directions. The ratios of total cross sections between T-VR and V-T increases as collision energy increases. Formation of azulene-argon complexes during the collision was observed at low enough collision energies. The complexes make only minor contributions to the measured translational to vibrational/rotational (T-VR) energy transfer.

Thermal Proton Transfer Reactions in Ultraviolet Matrix-Assisted Laser Desorption/Ionization

AbstractOne of the reasons that thermally induced reactions are not considered a crucial mechanism in ultraviolet matrix-assisted laser desorption ionization (UV-MALDI) is the low ion-to-neutral ratios. Large ion-to-neutral ratios (10–4) have been used to justify the unimportance of thermally induced reactions in UV-MALDI. Recent experimental measurements have shown that the upper limit of the total ion-to-neutral ratio is approximately 10–7 at a high laser fluence and less than 10–7 at a low laser fluence. Therefore, reexamining the possible contributions of thermally induced reactions in MALDI may be worthwhile. In this study, the concept of polar fluid was employed to explain the generation of primary ions in MALDI. A simple model, namely thermal proton transfer, was used to estimate the ion-to-neutral ratios in MALDI. We demonstrated that the theoretical calculations of ion-to-neutral ratios exhibit the same trend and similar orders of magnitude compared with those of experimental measurements. Although thermal proton transfer may not generate all of the ions observed in MALDI, the calculations demonstrated that thermally induced reactions play a crucial role in UV-MALDI. Figureᅟ